Process of flotation of minterals and ores

ABSTRACT

Process of froth flotation of oxide minerals which comprises using at least one of the following collector agents 1. MIXED SALTS OF AMMONIUM AND AMINES OF THE FORMULA: X(COONH4)2 (COOH.NR&#39;&#39;R&#39;&#39;&#39;&#39;R&#39;&#39;&#39;&#39;&#39;&#39;)2 2. ester-sulfonates of the formula: HX(COOR&#39;&#39;)(COOR&#39;&#39;&#39;&#39;)(COOR&#39;&#39;&#39;&#39;&#39;&#39;)(COOR&#39;&#39;&#39;&#39;&#39;&#39;&#39;&#39;)(SO3M) 3. ester amine salt sulfonates of the formula: HX(COOR)2(COOH.NR&#39;&#39;R&#39;&#39;&#39;&#39;R&#39;&#39;&#39;&#39;&#39;&#39;)2(SO3M) 4. sulfonates of mixed salts of ammonium and amines of the formula: HX(COONH4)2(COOH.NR&#39;&#39;R&#39;&#39;&#39;&#39;R&#39;&#39;&#39;&#39;&#39;&#39;)2(SO3M) in these formulae, X representing the hydrocarbon radical of the acid obtained by controlled pyrolysis of calcium citrate and acidification of the obtained pyrolysate; R being a C1-C20 alkyl radical; R&#39;&#39;, R&#39;&#39;&#39;&#39;, R&#39;&#39;&#39;&#39;&#39;&#39; and R&#39;&#39;&#39;&#39;&#39;&#39;&#39;&#39; being each hydrogen, C1-C20 alkyl, cycloalkyl, aralkyl, alkaryl or aryl, at least one of R&#39;&#39;, R&#39;&#39;&#39;&#39;, R&#39;&#39;&#39;&#39;&#39;&#39; and R&#39;&#39;&#39;&#39;&#39;&#39;&#39;&#39; being other than hydrogen and M being sodium, potassium or ammonium.

United States Patent [191 Verheyden et al.

[111 3,822,014 1 1 July 2,1974

[ PROCESS OF FLOTATION OF MINTERALS AND ORES [75] Inventors: Albert Verheyden, Gentstraat; Jean Hartmann, Rodenbachlaan, both of Belgium [73] Assignee: Citrex, Societe Anonyme,

Saint-Gilles-lez-Bruxelles, Belgium [22] Filed: Feb. 11, 1971 [21] Appl. No.: 114,613

[30] Foreign Application Priority Data OTHER PUBLICATIONS Chem. Abst., Vol. 66, 1967, 21197 X.

Primary Examiner-Robert Halper Attorney, Agent, or Firm-Wenderoth, Lind & Ponack [57] ABSTRACT Process of froth flotation of oxide minerals which comprises using at least one of the following collector agents 1. mixed salts of ammonium and amines of the formula:

2. ester-sulfonates of the formula:

3. ester amine salt sulfonates of the formula: HX(COOR) (COOH.NR'R"R") (SO M) 4. sulfonates of mixed salts of ammonium and amines of the formula: HX(COONH (COOH.NR'R"R") 3 in these formulae, X representing the hydrocarbon radical of the acid obtained by controlled pyrolysis of calcium citrate and acidification of the obtained pyrolysate; R being a C -C alkyl radical; R, R", R and R"" being each hydrogen, C,-C alkyl, cycloalkyl, aralkyl, alkaryl or aryl, at least one of R, R, R' and R" being other than hydrogen and M being sodium,

potassium or ammonium.

8 Claims, 4 Drawing Figures REAGENT NO. 6 lOOOg/TON RATE OF RECOVERY 1N O-CASSITERITEV QUARTZ MUSCOVITE PROCESS OF FLOTATION OF MIN'IERALS ORES The present invention is concerned with a new process for the flotation of minerals and ores, more particularly of oxide minerals and ores, in which a new class of collector is used.

By mineral is generally understood any natural inorganic substance that possesses a determined chemical composition and that has specific physical properties, whereas by ore is rather understood an inorganic substance extracted from the soil in order to isolate certain constituents, mostoften metallic substances, contained therein. For simplicity sake, in the present invention the two terms oreand mineral will be considered as equivalent and will therefore be used indiscriminately.

for obtaining concentrates from finely-ground ores.

They are all based on thedifference in wettability of 2 minerals that are artificially rendered water-repellant. Among these processes, froth flotation is by far the most widely used at the present time. It requires the use of special reagents which permit not only the separation of the useful minerals contained in the ore but also separation from one another of the various constituents of the ore. These reagents, which are generically called flotation agents, comprise collectors, frothers, and various modifying agents, such as depressants, activators, pH regulators and the like. Collectors are the main flotation agents because it is with the use thereof that a hydrophobic, film is formed on the particles of ore, thereby enabling them to be entrained by air bubbles, whereas the .gangue, on to which the collector is not fixed, retains its hydrophilic properties and, consequently remains within the aqueous suspension in which finally it forms a sediment.

Although a range of excellent collectors, including, in particular, the xanthates, is known for the enrichment of ores in sulfide minerals and native metals, the same is not true of nonsulfide ores, which are also known as oxide ores, on which the collectors used for sulfide minerals have practically no effect. Thus, in such cases it is necessary to adopt artifices, for example superficial sulfidation of the mineral to be subjected to flotation, with the aid of sodium sulfide, in order to impart to it a surface on which conventional sulfide mineral collectors can produce their waterproofing action and thereby ensure their entrainment by the air bubbles. Collectors are already known for oxide minerals, for example, fatty acids, fatty acid salts, amines and quarternary long carbon chain ammonium compounds containing 8 to 18 carbon atoms. However, these collectors do not give very good results. Certain minerals, such as cassiterite, are, in fact, not readily amenable to flotation and the recuperation rate of this mineral leaves much to be desired. It would, therefore, be very advantageous to extend the range of collectors utilisable for oxide minerals and to discover collectors which would be for oxide minerals what the xanthates are for of controlled pyrolysis of alkaline earth metal citrates,

preferably calcium citrate, at a temperature within the range of 230C to 400C, in which alkaline earth metal salts, preferably calcium salts of an unsaturated polycarboxylic acid of unknown chemical structure, are obtained. It is known, however, that this acid contains a hydrocarbon chain carrying four carboxyl groups and a carbon-carbon double bond. In this same Patent Specification there is described a series of products derived from this fundamental acid and which are classified into two categories: a first category, in which the carbon-carbon double bond of the acid is retained and the carboxyl groups are converted into esters and/or salts by reaction, respectively, with various alcohols and/or inorganic and/or organic bases; and a second category in which the double bond disappears by reaction'with the bisulfite ion in order to produce a tetracarboxylic sulfonic acid in which the SO3H group is formed into asalt by an inorganic or an organic base and the carboxyl groups are formed into esters and/or salts, respectively, with various alcohols and/or inorganic and/or organic bases. This Patent Specification mentions the following applications for the products obtained in this manner: alimentary acidulants, synthesis of products rich in calcium which can be used in pharmaceuticals, agents forthe solubilisation of certain sparingly soluble salts, condensation polymers for plastics materials and ion exchangers.

According to the present invention, we have found that certain of the compounds mentioned in British Pat. Specification No 1,082,179 are excellent collectors for ores and minerals, particularly for oxide ores and minerals.

It is, therefore, an object of the present invention to provide a process for the flotation of minerals and ores,

particularly oxide minerals and ores, which is charac-' terised in that at least one of the following compounds is used as flotation collector agent: 1. mixed salts of ammonium and amines of the general formula:

2. ester-sulfonates of the general formula:

HX(COOR')(COO ")(COOR')(COOR")- ($0 M) ll 3. ester amine salt sulfonates of the general formula:

HX(COOR) (CO0H.HR'R"R') (SO M) Ill 4. sulfonates of mixed salts of ammonium and amines of the general formula:

in these formulae, X represents the hydrocarbon radical of the acid obtained by controlled pyrolysis of calcium citrate and acidification of the obtained pyrolysate; R is a C C alkyl radical; R, [R'', RR" and R which may be the same or different, are hydrogen atoms or C -C alkyl radicals or cycloalkyl, aralkyl, alkaryl or aryl radicals, at least one of R, R", R'R" and R"" being other than hydrogen; and M is sodium, potassium or ammonium.

The preparation of the acid obtained by controlled pyrolysis of calcium citrate, and also the derivatives of this acid corresponding to general formulae (1) to (IV) above, has been described in detail in British Pat. Specification No 1,082,179; reference should, therefore, be made to this Patent Specification for details of their preparation.

In Table l below, there is given, by way of example, a list of 15 compounds to be used according to the present invention, which correspond to one of the general formulae l) to (IV) given above. In this Table, the first the form of oxides, hydroxides, carbonates, silicates or the like. The expression metallic oxide ores is sometimes reserved for minerals or natural mixtures of minerals from which one or more metals are extracted for column headded reagent corresponds to the number 5 metallurgical purposes, and the expression non metalby which each of these compounds is designated in ablic oxide ores" for minerals or natural mixtures of minbreviated form in the Examples of application given erals which are used for non-metallurgical purposes. It later on. The second column indicates the number of frequently happens, however, that these oxide ores the general formula of each reagent. In the following and/r minerals correspond to both of the above definicolumns, there are given the meanings of the symbol 10 trons simultaneously, as for example in the case of ru- R, R, R", R', R"" and M used in the general f rmutile, which is used not only as an ore from which metallae (I) to (IV) mentioned above. lic titanium is extracted but also as a white pigment for TABLE I Reagent Formula R R R" R R"" M l I H H n-dodecyl' NH, 2 ll n-butyl n-butyl n-butyl n-butyl Na 3 II 2-ethyl 2-ethyln-butyl n-butyl Na hexyl hexyl 4 ll n-butyl n-butyl alkyl alkyl" Na 5 ll n-butyl n-butyl alkyl" alkyl" Na 6 ll n-butyl n-butyl lauryl lauryl Na 7 II n-butyl lauryl lauryl lauryl Na 8 ll n-butyl n-butyl stearyl stearyl Na 9 II n-butyl n-butyl benzyl benzyl Na 10 ll n-butyl n butyl fl-phenylfl-phenyl- Na ethyl ethyl l I ll alkyl' alkyl alkyl alkyl Na 12 ll H H alkyl" alkyl" Na 13 Ill n-butyl phenyl H H NH, 14 Ill n-butyl cyclo- H H NH.

hexyl 15 IV H H n-dodecyl NH,

a. The n-dodecyl radical derived from commercial n-dodecylamine ARMEEN k2 D sold by ARMOUR Co.

h. The alkyl is the residue of a C,,-C technical alcohol. 0. The alkyl is the residue of a C C technical alcohol. d. The alkyl is the residue of a (I -C technical alcohol.

The quantities of'ciiibeiini'or generalformulae (I) paints, enamels and the like in the form of titanium dito (IV) used for the flotation of ores will obviously vary, depending upon the specific compounds used and also upon the nature of the ore to be treated, the auxiliary agents used, the pH and the like. Nevertheless, they are generally used in amounts of between 300 and 40 4,000 g. per ton of ore treated, preferably in amounts of 500 to 1,000 g. per ton of ore.

As previously hentiafiafme compounds used according to the present invention are particularly suitable for the flotation of oxide minerals, in other words minerals which are not in the form of native elements, of sulfides, arsenides, antimonides or the like but are in Oxide minerals of:

Iron:

oxide. It is for this reason that, for the sake of simplicity, the expressions oxide ores" will be used hereinbelow to designate all these natural mineral substances. In addition, minerals such as fluorspar or cryolite will also be considered as oxide minerals, although they do not contain oxygen. Similary, minerals such as barytine, i.e., borium sulfate, which contains sulfur in the form of sulfate (and not in the form of sulfide) will also be considered as oxide minerals. There is given below a non-limiting list of oxide ores and minerals which may be treated by flotation by using, as collectors, the compounds of general formulae (I) to (IV) according to the present invention.

limonite, haematite, oligiste magnetite. lepidocrocite.

siderite, chamosite, goethite;

Manganese:

pyrolusite (polyanite), psilomelane, manganite, braunite,

hausmannite, rhodonite. dialogite (rhodocrosite), tephroite, franklinite, huebnerite, asbolane, wad;

Lead: Zinc:

cerusite, anglesite. pyromorphitc. crocoite; smtthsomte. wlllemlte, zmclte. hydrozmclte, hemlmorplute (calamine). franklinite. troostite:

atacamite. chrysoculle. dioptasc. chalkunthite, turquoise;

cassiterite. thoreaulite. nordens k tloeldite. arandisite.

nlgeritc. frunckclte. souxite (var amoffite);

Titanium:

ilmenite. rutlle. brookite, analase. titanitc (sphenc).

perowskite:

Molybdenum: Tungsten:

(ferri)molybdite, owellitc, wulfcnitc; woltrumitc. schce rte. ferberite. hucbnerite. reinitc. stolzite;

4 Continued Oxide minerals of:

Vanadium:

Zirconium: Beryllium:

Tantalum and Niobium:

carnotite, tyuyamanite, descloizite, cuprodescloizite (mottramite), roscoelite, vanadinite, sengierite', psittacinite;

zircon. baddeleyite, zircite, zirkelite, eudialyte;

beryl, bertrandite, phenacite, beryllonite, chrysoberyl, euclase;

colombites, tantalites, colombotantalites,

pyrochlore, microlite, simpsonite, samarskite,

fergu sonite, formanite, euxenite, polycrase, tapiolite, mossite, dysanalyte, betafite, yttrotantalite;

Rare earth metals:

'monazite, bastnaesite, xenotime, gadolinite,

euxenite, thorite. allanite, cerite, parisite;

Various oxide minerals:

quartz, feldspare, fluorite (fluorapar), micas (musco- Vite,

biotite, phlogopite, lepidolite), disthene, sillimanite,

phosphorite, asbestos (tremolite, chrysotile, amosite, actinolite), barytine,

witherite,

graphite, borax, gypsum, wollastonite, various ochres and the like.

The collectors used according to the present invention can be used in all flotation equipment normally employed. For the experiments described in the Examples given below, use was made of Fagergren type cells but it is obvious that any other cell enabling froth flotation to be carried out could be suitable (see, for exam ple, Kirk-Othmer, Encyclopaedia of Chemical Technology, 2nd edition, volume 9, (l966),p.392).

In general, the collectors of the present invention are used at ambient temperature but, nevertheless, operation at an elevated temperature for particular separation operations may be contemplated.

As in all flotation processes, the pH is of decisive importance in the preparation of ores. Since the composition of ores varies considerably from one deposit to another, and even within the same deposit, it is, therefore, necessary to determine for each ore or mineral and for each particular collector, the pH which permits the best separation of the components of the ore. Some gr aphs are shown in the accompanying drawings which illustrate the collector power of the compounds used according to the present invention in dependance upon the pH for certain minerals. In order to acidify the slurry, an inorganic acid is ordinarily added, particularly sulfuric acid because of its low cost. In order to,

render the slurry alkaline, it is possible to use basic substances, for example, sodium hydroxide, sodium carbonate, calcium hydroxide or the like.

An advantage of the compounds used according to the present invention is that most of them possess frothing properties so that the use of frothing agents can frequently be dispensed with. Nevertheless, it may happen that an additional frothing agent will be necessary and, in this case, pine oil, camphor oil, cresylic acid, higher alcohols, higher ether-alcohols, non-ionic surfactants, amines or the like may be used as frothing agents.

Similarly, the compoundsused according to the present invention may be used together with conventional reagents used in flotation, particularly ordinary collectors for oxide minerals, for example, fatty acids, fatty acid salts, alkylsulfates, alkylarylsulfonates, phosphonic and arsenic homologues, amines or quaternary long chain. ammonium compounds containing eight to 18 carbon atoms. Other auxiliary flotation agents which may be used are depressants, activators, precipitation agents, dispersing agents, organic colloidal materials and the like.

In the flotation process according to the present in vention, the crushed ore or mineral (400 microns to 5 microns) is added to water so that the resulting slurry contains about 10 to 40 percent of said ore or mineral. The pH of the slurry is then adjusted by suitable addition of acid or alkali and the collector or collectors according to the present invention and optionally the auxiliary flotation agents mentioned above is or are introduced. Not more than about 3 minutes are needed for the slurry to be conditioned and then air is injected into the slurry in order to produce a froth which, by flotation becomes charged with concentrated ore. This is then collected. The discontinuous flotation operation lasts, on average, less than 15 minutes.

The advantages of the collectors used according to the present invention are numerous and substantial. In the first place, they are very effective for the concen tration of oxide ores which hitherto were not very suit able for the flotation technique; Thus, in the particular case of the flotation of cassiterite, the results obtained according to the process of the present invention are far better than those mentioned in recent literature (cf. Kirchberg, Chem.Abstracts,7l,63305; Toepfer and Bilsing, Chem.Abstr.7l,63306; Collins, Trans.Inst- .Min.Metall.(sect.C, Mineral Process Extr.Metall),

76,.lune 1967,C7793; lnst.Mining & Metallurgy, No 736, C l to 13). The process of the present invention permits the flotation of cassiterite under far better conditions, both as regards the content of the concentrate or concentrates and the rate of recuperation and as regards convenience of performance (no preliminary treatment is required).

Secondly, the collectors used according to the present invention are inexpensive products which are obtained from an acid produced by pyrolysis of calcium citrate, which is a readily available commercial product, and also from esterification alcohols and from amines or salt-producing bases, which are commercially freely available.

Thirdly, the chemical composition of the collectors may be varied infinitely by modifying the nature and proportion of the salt forming and/or ester forming agents, which makes it possible to obtain a sulficiently wide range of collectors to meet the most difficult flotation requirements.

Finally, we have found that the association of two or more of the collectors used according to the present invention sometimes makes it possible to obtain better results than those obtained with each collector used separately (see Example 7).

The following Examples are given for the purpose of illustrating the present invention. In these Examples, the flotation is carried out in a Fagergren cell. The solids content of the slurry is about percent by weight and the conditioning time is 2 to 3 minutes: the pH is first adjusted and then the collector is added. The flotation time is the time required for the exhaustion of the mineralised froth; on average, it is less than 15 minutes. The ores and minerals used in the tests are, in some cases, pure naturel mineralogical species and sometimes run of mine ores.

Example 1.

A pegmatite-greisen originating from Katanga is subjected to flotation. This ore is rich in cassiterite; the gangue is composed mainly of quartz and muscovite but it also contains feldspar and tourmaline.

Using as collector the reagent N6 indicated in Table I at the rate of 500 g. per ton (pH 5.6), the SnO recovery rate is 97.5 percent; the concentrate obtained titrates at 55.6 percent SnO whereas the original titration of the ore was 8.9 percent SnO In a similar test with an ore from the same deposit but having a lower SnO content (0.24 percent) and a high mica content, the recovery rate reaches 100 percent and the concentrate obtained titrates at 28 percent SnO Example 2.

Using reagent N"6 at the rate of 2,000 g. per ton (pH 4.7), an eluvial colombo-tantalite from Katanga, containing quartz, iron oxides and hydroxides, ilmenite,

zirconium and the like, is subjected "as flotation.

Whereas the original (Nb,Ta) O content of the ore was 0.4 percent, a concentrate containing 6.6 percent is obtained, with a recovery rate of 98.8 percent. Example 3.

Using reagent N6 at the rate of 1,000 g. per ton (pH 8.9) for the flotation of a vein-bearing fluorspar with partially silicified calcareous gangue, having an initial CaF content of 37.0 percent, a concentrate is obtained with a CaF content of 80.4 percent at a recovery rate of 99.7 percent.

Example 4.

Using reagent N3 (500 g. per ton, pH 6.7) as collector, the portion rich in barium sulfate of a quartz and barytine vein, worked in France, is subjected to flotation.

The concentrate obtained titrates at 93.9 percent BaSO whereas theuntreated ore titrated at 77.8 percent. The recovery rate is 96.2 percent.

A batch of barytine from the same deposit but of poorer quality (BaSO 39.0 percent) is subjected to flotation. The collector is the same reagent N 3, likewise used at the rate of 500 g. per ton (pH 5.6). Re-

concentrate is 83.1 percent. Example 5.

Reagent N 3 is used at the rate of 1,000 g. per ton (pH 6.3) to treat the same fluorspar as in Example 3. A concentrate containing 78.5 percent of CaF is obtained with a recovery rate of 98.0 percent.

Example 6.

Reagent N 10 is used (500 g. per ton, pH 7.6) to treat a Belgian vein-bearing barytine with quartz gangue, containing significant quantities of calcite, pyrites, blende and galena. Despite the complexity of the ore treated, it was possible to obtain a concentrate titrating at 63.7 percent BaSO, with a recovery rate of 75.2 percent, whereas the original BaSO, content was 45.0 percent.

Example 7.

A l/l mixture of reagents N 2 and N 8 is used at the rate of 2,000 g. per ton for the flotation of a North African carbonated zinc-lead ore (smithsonite-cerusite). The pH is adjusted to 7.4.

The lead content, which is 10.3 percent in the initial ore, reaches 33.6 percent in the concentrate, whereas the zinc content falls from 20.4 percent to 11.2 percent. The lead recovery rate is 69.2 percent.

Example 8.

In the Table below, some cases of flotation of ores and minerals are mentioned in which the collectors according to the present invention are used. Column A indicates the ores and minerals which can be subjected to flotation with the reagents, while column B indicates those which cannot be treated in this way.

Reagent No.

@ JIA cerusite, smithsonite, malachite barytine, fluorspar, wolframite calcite, pyrite, galena quartz, feldspar, muscovite,

calcite quartz, feldspar quartz quartz quartz, feldspar, muscovite -Continued Reagent No. A B

7 beryl quartz U 8 pyrolusite, barytine malachite 9 rutile, cerusite, smithsonite quartz, calcite, feldspar,

pyrites l rutile, pyrolusite, barytine. quartz, feldspar, pyrites cerusite, smithsonite, malachite l l malachite dolomite, calcite l2 haematite silica l3 fluorspar, cerusite, smithsonitc quartz, calcite l4 cerusite, smithsonite quartz, calcite, galena,

blende l5 smithsonite, quartz calcite, beryl Example 9. 5 to flotation.

In this Example, reference is made to the accompanying graphs of the accompanying drawings, which show the influence of the pH on the collector power of certain compounds used according to the present invention in relation to certain minerals and the technical effects which can be obtained with them.

In FIG. 1, the behaviour of reagent N6 is examined in dependence upon the pH for the three minerals cassiterite, quartz and muscovite.

It can be seen that this reagent, when used at a rate of 1,000 g. per ton and with a pH close to 7, gives a cassiterite recovery rate of 99.4 percent, whereas with the same pH this rate for quartz is 0 percent and for muscovite is 26.0 percent. This explains the excellentflotation results indicated in Example 1 in connection with a pegmatite-greisen from Katanga, the main constituents of which are cassiterite, quartz and mica.

In FIG. 2, there is indicated the behaviour of reagent N 2 in dependence upon the pH for the two minerals fluorspar and calcite. At the rate of 1,000 g. per ton and with a pH of about 6, the recovery rate for fluorspar is 88.3 percent, whereas that for calcite under the same conditions is practically nil. Results comparable with those given in Example 3, where reagent N"6 was used, are thus obtained here. The two reagents N2 and N6 are, therefore, excellent collectors for the recuperation of fluorspar from calcareous gangue fluorspars.

In FIG. 3, there is indicated the behaviour of reagent N3 in dependence upon the pH for the two minerals barytine and quartz. At the rate of 1,000 g. per ton and with a pH close to 7, the recovery rate for barytine is practically quantitative, whereas that for quartz under the same conditions is practically nil. This explains the possibility of excellent separation of barytine, as shown in Example 4.

In FIG. 4 there is illustrated an example of inverse flotation in which the desired ore (beryl) sinks, while the gangue (quartz) floats.

With reagent Nl5, used at the rate of 1,000 g. per ton and with a pH of 4.8, the rate of recovery ofquartz by flotation amounts to 93.5 percent, whereas under the same conditions, that of beryl is only 11 percent. Example 10 A copper ore from Katanga (malachite with a dolornitie gangue), titrating 5.7 percent Cu, is subjected to flotation.

Reagent Nll cited in Table I is used at the rate of 500 g/ton (pH 5.6). I

The copper recovery rate is 66 percent and the concentrate obtained titrates at 27 percent Cu.

Example 11 An itabirite containing percent Fe, mainly in the form of haematite with a siliceous gangue is subjected Reagent N 12 mentioned in Table l is used at the rate of 500 g/ton (pH 5.6).

The iron recovery rate is 68 percent and the concentrate obtained titrates at 63 percent Fe.

We claim:

' 1. A process of flotating non-sulfide minerals and ores wherein use is made of collector agents, which comprises using as collector agents at least one member selected from the group consisting of:

mula: X(COONH (COOH'NRR? 'R' 2. ester-sulfonates of the formula: HX(COOR') (COOR") (COOR"') (COOlR' ($0 M) 3. ester amine salt sulfonates of the formula: HX(CO- OR) (COOH'NR'R"R') (SO M) and 4. sulfonates of mixed salts of ammonium and amines of the formula: l-IX(COONH.,)

(COOH'NR'R"R"') (SO M) wherein in the above formulas, X respresents the hydrocarbon radical of the acid obtained by controlled pyrolysis of calcium citrate at a temperature within the range of 230C to 400C and acidification of the obtained pyrolysate; R is a C,-C alkyl radical; R, R", R and R"" is a member selected from the group consisting of hydrogen atoms and C,-C alkyl, cycloalkyl, aralkyl, alkaryl and aryl radicals, at least one of R, R", R and R being other than hydrogen and wherein M is a member selected from the group consisting of sodium, potassium and ammonium.

2. A process according to claim l,'in which the collector agents are used in amounts of 300 to 4,000 g. per ton of mineral or ore.

3. A process according to claim. 1, in which the collector agents are used in amounts of 500 to 1,000 g. per

- ton of mineral or ore.

4. A process according to claim 1, in which the collector agents are used at ambient temperature.

5. A process according to claim 1, in which the collector agents are used at a temperature higher than ambient temperature.

6. A process according to claim 1, in which the collector agents are used at a pH of at most 7.

7. A process according to claim 1, in which the collector agents are used at a pH of at least 7.

8. A process according to claim 1, in which the collector agents are used together with products selected from the group consisting of ordinary collector agents not according to the invention, frothing agents, depressants, activators, precipitation agents, and dispersing agents.

1. mixed salts of ammonium and amines of the for- 

1. MIXED SALTS OF AMMONIUM AND AMINES OF THE FORMULA: X(COONH4)2 (COOH.NR''R"R''")2
 2. ESTER-SULFONATES OF THE FORMULA: HX(COOR'')(COOR")(COOR"'')(COOR"")(SO3M)
 2. A process according to claim 1, in which the collector agents are used in amounts of 300 to 4,000 g. per ton of mineral or ore.
 2. ester-sulfonates of the formula: HX(COOR'') (COOR'''') (COOR'''''') (COOR'''''''') SO3M)
 3. ester amine salt sulfonates of the formula: HX(COOR)2(COOH.NR''R''''R'''''')2(SO3M) and
 3. A process according to claim 1, in which the collector agents are used in amounts of 500 to 1,000 g. per ton of mineral or ore.
 3. ESTER AMINE SALT SULFONATES OF THE FORMULA: HX(COOR)2(COOH.NR''R"R"'')2(SO3M)
 4. SULFONATES OF MIXED SALTS OF AMMONOUM AND AMINES OF THE FORMULA: HX(COONH4)2(COOH.NR''R"R"'')2(SO3M) IN THESE FORMULAE, X REPRESENTING THE HYDROCARBON RADICAL OF THE ACID OBTAINED BY CONTROLLED PYROLYSIS OF CALCIUM CITRATE AND ACIDIFICATION OF THE OBTAINED PYROLYSATE; R BEING A C1-C20 ALKYL RADICAL; R'', R", R"'', AND R"" BEING EACH HYDROGEN, C1C20 ALKYL CYCLOALKYL, ARALKYL, ALKARYL OR ARYL, AT LEAST ONE OF R R'', R", R"'' AND R"" BEING OTHER THAN HYDROGEN AND M BEING SODIUM, POTASSIUM OR AMMONIUM.
 4. A process according to claim 1, in which the collector agents are used at ambient temperature.
 4. sulfonates of mixed salts of ammonium and amines of the formula: HX(COONH4)2(COOH.NR''R''''R'''''')2(SO3M) wherein in the above formulas, X respresents the hydrocarbon radical of the acid obtained by controlled pyrolysis of calcium citrate at a temperature within the range of 230*C to 400*C and acidification of the obtained pyrolysate; R is a C1-C20 alkyl radical; R'', R'''', R'''''' and R'''''''' is a member selected from the group consisting of hydrogen atoms and C1-C20 alkyl, cycloalkyl, aralkyl, alkaryl and aryl radicals, at least one of R'', R'''', R'''''' and R'''''''' being other than hydrogen and wherein M is a member selected from the group consisting of sodium, potassium and ammonium.
 5. A process according to claim 1, in which the collector Agents are used at a temperature higher than ambient temperature.
 6. A process according to claim 1, in which the collector agents are used at a pH of at most
 7. 7. A process according to claim 1, in which the collector agents are used at a pH of at least
 7. 8. A process according to claim 1, in which the collector agents are used together with products selected from the group consisting of ordinary collector agents not according to the invention, frothing agents, depressants, activators, precipitation agents, and dispersing agents. 